US4978807A - Method for the preparation of methyl tertiary butyl ether - Google Patents

Method for the preparation of methyl tertiary butyl ether Download PDF

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Publication number
US4978807A
US4978807A US07/373,232 US37323289A US4978807A US 4978807 A US4978807 A US 4978807A US 37323289 A US37323289 A US 37323289A US 4978807 A US4978807 A US 4978807A
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United States
Prior art keywords
distillation
zone
reaction
isobutene
methanol
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US07/373,232
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English (en)
Inventor
Lawrence A. Smith, Jr.
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Catalytic Distillation Technologies
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Chemical Research and Licensing Co
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Assigned to CHEMICAL RESEARCH & LICENSING COMPANY reassignment CHEMICAL RESEARCH & LICENSING COMPANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SMITH, LAWRENCE A. JR.
Priority to US07/373,232 priority Critical patent/US4978807A/en
Priority to MX020428A priority patent/MX167454B/es
Priority to KR1019900005899A priority patent/KR0148013B1/ko
Priority to ES90306322T priority patent/ES2057407T3/es
Priority to EP90306322A priority patent/EP0405781B1/de
Priority to DE69011434T priority patent/DE69011434T2/de
Priority to JP2165507A priority patent/JP2807314B2/ja
Publication of US4978807A publication Critical patent/US4978807A/en
Application granted granted Critical
Assigned to CATALYTIC DISTILLATION TECHNOLOGIES reassignment CATALYTIC DISTILLATION TECHNOLOGIES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHEMICAL RESEARCH & LICENSING COMPANY
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/42—Regulation; Control
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
    • C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/03—Ethers having all ether-oxygen atoms bound to acyclic carbon atoms
    • C07C43/04—Saturated ethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S203/00—Distillation: processes, separatory
    • Y10S203/06—Reactor-distillation

Definitions

  • the present invention relates to an improvement in the manner of conducting concurrent reactions and distillations wherein the catalyst is also the distillation structure.
  • a preferred and commercial catalyst structure described in the above patents comprises a cloth belt with a plurality of pockets spaced along the belt and containing particulate catalyst material, said cloth belt being wound in a helix about a spacing material such as stainless steel knitted mesh. These units are then disposed in the distillation column reactor.
  • a spacing material such as stainless steel knitted mesh.
  • the distillation parts of the above disclosures have been conventional, i.e., counter-current vapor liquid flow in the packed catalyst bed with the catalyst acting as the contact structure, at least in the reaction zone.
  • the reaction zone having the catalyst packing is designated the reaction distillation zone to distinguish it from other distillation zones which contain either inert packing or conventional distillation trays.
  • the conventional distillation zones may be above or below the distillation reaction zone according to the separation desired.
  • the physical embodiment of the distillation column reactor includes a separate distillation zone below the distillation reaction zone to insure that the unreacted feed components are removed from the ether product which is taken off as bottoms product.
  • the lower distillation zone is a separate distillation column connected to another distillation column which contains the catalyst. Vapor and liquid flow lines are provided so that essentially the two columns act as one.
  • the present invention is the discovery that the reaction rate can be increased by improving the contact of the liquid with the catalyst, which is accomplished by increasing the liquid level in the reaction distillation zone.
  • a liquid flow restrictor between the distillation reaction zone and the lower distillation zone. That is, the vapor from below may rise up to (and through) the reaction distillation zone as in a conventional or prior operation but a portion of the liquid is maintained there.
  • a single distillation column reactor is used, a conventional distillation tray with the downcomer area blocked is located between the reaction distillation zone and the distillation zone.
  • a by pass line for liquid flow is provided about the tray and a valve is provided in the liquid flow conduit to restrict liquid downflow and thereby to build up a liquid level above that tray just below the catalyst bed.
  • a perforated plate may be used to support the catalyst and cause a liquid pressure drop in the column thus building up a level in the catalyst. If the two column system is used, then a valve or other restriction means is placed in the liquid flow line between the two columns.
  • liquid level is used herein to mean an increased density of the material in the reaction distillation zone over that of a pure distillation as distinguished to a continuous liquid phase.
  • the phase system as present in the reaction distillation zone is physically a froth. This is the result of the vapor traveling up through the liquid retained in the zone.
  • FIG. 1 is a flow diagram of one embodiment of the invention showing separate columns for the distillation and reaction zones.
  • FIG. 2 is a plan view of the liquid flow restriction in a single column.
  • FIG. 3 is top view of a perforated plate useful in the column of FIG. 2.
  • FIG. 1 shows a simple flow diagram of a process using the present invention.
  • the particular process shown is for the production of methyl tertiary butyl ether (MTBE) from the reaction of methanol and isobutene in a mixed butene/butane feed stream.
  • MTBE methyl tertiary butyl ether
  • U.S. Pat. No. 4,307,254 which is herein incorporated by reference.
  • a first distillation column 1 which contains an acid cation exchange resin packing 7 suitable for the reaction.
  • the acid cation exchange resin catalyst 7 is suitably disposed in the column 1 as described in U.S. Pat. No. 4,307,254 to act as both a catalyst and distillation structure.
  • the methanol and mixed butene/butane stream is fed to the first column 1 into the catalyst 7 in a feed zone via flow lines 5 and 6.
  • the methanol reacts with the isobutene in the catalyst bed or reaction distillation zone to form MTBE.
  • the unreacted components of the mixed butene/butane stream are distilled off overhead and recovered via flow line 8.
  • the MTBE product is distilled off toward the bottom since the temperature of the catalyst (reaction distillation) zone is maintained at the boiling of the reactants at the operating pressure of the column, which is lower than the boiling point of the MTBE.
  • the bottoms liquid product containing MTBE and some dissolved unreacted methanol and C 4 hydrocarbons is carried out the bottom of the first column 1 via flow line 3 to the top of second column 2 where the MTBE is more completely separated from any dissolved methanol or C 4 's in a conventional distillation column 2 having trays as shown or inert packing and recovered via flow line 9.
  • the unreacted materials are recovered overhead via flow line 4 which carries them back as vapors to the bottom of the first column 1.
  • a level controller 10 is secured to the first column 1 and senses a liquid level in the first column 1 (as by a differential pressure) and operates flow control valve 11 which acts as a liquid flow restriction between the two columns and maintains a desired preset liquid level in the catalyst bed 7 of column 1. Note the level control 10 may be positioned to detect the level over any portion of the column 1.
  • Example I shows a comparison of one such unit operated with and without the liquid level in the catalyst bed.
  • FIG. 2 illustrates an arrangement which may be used if only one column is used. Only that portion of the column is illustrated that is used to maintain the liquid level in the catalyst bed.
  • the column 200 has a bed of catalyst 201 which acts as a distillation structure.
  • a perforated plate 202 which supports the catalyst bed 201.
  • the plate 202 as indicated in FIG. 3 is perforated to allow gas passage upward into the catalyst bed 201 yet provides a sufficient pressure drop to allow a liquid level to build up above the plate in the bed 201.
  • the plate is approximately 5-20 percent open space.
  • a liquid bypass flow line 203 is provided about the plate 202 to give added control of the level.
  • Valve 204 in bypass 203 may be opened or closed in response to a differential pressure (indicating liquid level) to control the liquid level. If desired the valve can be part of a control loop (not shown) responding to a liquid level controller.
  • a standard distillation tray may be substituted for the perforated plate 202.
  • the downcomer area of the standard tray is blocked and the by pass flow line 203 used to control the liquid level in the bed.
  • a commercial catalytic distillation process for the production of MTBE was operated according to that disclosed in U.S. Pat. No. 4,307,254. Following an incident in which the catalyst was partially deactivated, the operation was changed to maintain the liquid level at the top of the catalyst zone. The arrangement was similar to that shown in FIG. 1. A control valve acted as a restriction in the liquid flow line 3 to control the liquid level which was sensed by a differential pressure in the distillation reaction column 1. Unexpectedly, the performance of the commercial unit with the damaged catalyst was almost equal to the unit with undamaged catalyst.
  • the method and structure have been found to be particularly useful for conducting the catalytic distillation production of tertiary butyl alcohol (TBA) from the hydration of isobutylene.
  • TBA tertiary butyl alcohol
  • a stream containing isobutylene is fed to the column below the catalyst bed and water is fed above the catalyst bed.
  • the catalyst bed contains an acid cation exchange resin as described in U.S. Pat. 4,307,254 and is placed into the one inch laboratory column in the manner described therein. Unreacted butylene, water and inerts (such as other C 4 's) are taken overhead and the TBA product is recovered as bottoms.
  • Water must be present in amounts sufficient to maintain the catalyst in a hydrated state plus enough for the reaction and to accommodate the water azeotropes in the system.
  • One method of control is to measure the amount of water present in the TBA fraction within the column and to maintain that amount above zero but below the azeotropic concentration at the temperature and pressure used.
  • the catalyst performs satisfactorily at first but quickly loses its selectivity due to loss of water despite the control technique outlined above. This may be attributed to mass transfer and distribution problems within the catalyst bed. It has been found that maintaining a liquid level in the catalyst bed using the technique of FIGS. 2 and 3 maintains the wetted state of the catalyst and allows high selectivity toward tertiary butyl alcohol production. Table I below compares the results of the process with and without the liquid level in the bed. The liquid level in the catalyst bed is indicated by the high differential pressure across the bed. In the test runs, a 1" diameter tower was used ten feet in length. Four feet of Rohm and Haas Amberlyst 15 catalyst was inserted into the column in a pocketed belt twisted with wire mesh.
  • pilot plant was run as described in commonly assigned U.S. Pat. application Ser. No. 122,485 filed 11/16/87 using a 3" pilot plant column with Union Carbide LZY-82 molecular sieve in the pockets of the catalyst structure for the production of cumene form the alkylation of benzene with propylene.
  • the use of the liquid level as measured by the differential pressure across the bed improved performance of the catalyst and process. Table II below shows comparative data between the normal operation and with the liquid level.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
US07/373,232 1989-03-23 1989-06-29 Method for the preparation of methyl tertiary butyl ether Expired - Lifetime US4978807A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US07/373,232 US4978807A (en) 1989-03-23 1989-06-29 Method for the preparation of methyl tertiary butyl ether
MX020428A MX167454B (es) 1989-06-29 1990-04-23 Metodo para la preparacion de eter metil terbutilico
KR1019900005899A KR0148013B1 (ko) 1989-06-29 1990-04-26 촉매증류 공정을 수행하기 위한 장치, 그것의 조작방법 및 그를 이용하여 메틸3차 부틸에테르를 제조하는 방법
EP90306322A EP0405781B1 (de) 1989-06-29 1990-06-11 Verfahren und Vorrichtung zur Herstellung von Methyl-tertiär-Butylether
ES90306322T ES2057407T3 (es) 1989-06-29 1990-06-11 Metodo y aparato para la preparacion de metil-terbutil-eter.
DE69011434T DE69011434T2 (de) 1989-06-29 1990-06-11 Verfahren und Vorrichtung zur Herstellung von Methyl-tertiär-Butylether.
JP2165507A JP2807314B2 (ja) 1989-06-29 1990-06-22 メチル ｔ―ブチルエーテルの製造法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32848789A 1989-03-23 1989-03-23
US07/373,232 US4978807A (en) 1989-03-23 1989-06-29 Method for the preparation of methyl tertiary butyl ether

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US (1) US4978807A (de)
EP (1) EP0405781B1 (de)
JP (1) JP2807314B2 (de)
KR (1) KR0148013B1 (de)
DE (1) DE69011434T2 (de)
ES (1) ES2057407T3 (de)
MX (1) MX167454B (de)

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5113015A (en) * 1990-11-20 1992-05-12 Amoco Corporation Recovery of acetic acid from methyl acetate
US5120403A (en) * 1989-03-23 1992-06-09 Chemical Research & Licensing Company Method for operating a catalytic distillation process
US5149892A (en) * 1991-10-22 1992-09-22 Ppg Industries, Inc. Chlorinated benzenes
US5221441A (en) * 1989-03-23 1993-06-22 Chemical Research & Licensing Company Method for operating a catalytic distillation process
EP0556025A1 (de) 1992-02-10 1993-08-18 Chemical Research & Licensing Company Selektiven Hydrierung von C5-Schnitten
US5248837A (en) * 1992-10-21 1993-09-28 Chemical Research & Licensing Company Method for controlling catalytic distillation etherifications
US5262576A (en) * 1989-03-23 1993-11-16 Chemical Research & Licensing Company Method for the alkylation of organic aromatic compounds
WO1994008681A1 (en) * 1992-10-16 1994-04-28 Koch Engineering Company, Inc. Catalytic reaction and mass transfer structure and process employing same
US5489719A (en) * 1992-06-02 1996-02-06 Mobil Oil Corporation Process for the production of tertiary alkyl ether rich FCC gasoline
US5550298A (en) * 1988-09-02 1996-08-27 Sulzer Brothers Limited Device for carrying out catalyzed reactions
US5565068A (en) * 1994-02-28 1996-10-15 Texaco Development Corporation Energy conservation during plural stage distillation
US5628880A (en) * 1996-02-12 1997-05-13 Chemical Research & Licensing Company Etherification--hydrogenation process
AU679876B2 (en) * 1995-07-26 1997-07-10 Phillips Petroleum Company A method for improving the recovery of ethanol contained in an etherification reaction zone product stream
US5770782A (en) * 1996-02-08 1998-06-23 Huntsman Petrochemical Corporation Process and system for alkylation of aromatic compounds
US5777187A (en) * 1996-02-08 1998-07-07 Huntsman Petrochemical Corporation Two-step process for alkylation of benzene to form linear alkylbenzenes
US5919989A (en) * 1996-07-16 1999-07-06 Catalytic Distillation Technologies Etherification process
US6133492A (en) * 1996-02-08 2000-10-17 Huntsman Petrochemical Corporation Alkylation of benzene to form linear alkylbenzenes using fluorine-containing mordenites
US6166281A (en) * 1996-02-08 2000-12-26 Huntsman Petrochemical Corporation Alkylation of benzene to form linear alkylbenzenes using fluorine-containing mordenites
US6846959B2 (en) 2002-10-07 2005-01-25 Air Products And Chemicals, Inc. Process for producing alkanolamines
US20060030741A1 (en) * 2004-08-05 2006-02-09 Catalytic Distillation Technologies Etherification process
US20060235092A1 (en) * 2002-02-22 2006-10-19 Catalytic Distillation Technologies Liquid-continuous column distillation
US7348465B2 (en) 2005-02-08 2008-03-25 Shell Oil Company Selective alkylation of aromatic hydrocarbons
US9260357B2 (en) 2012-07-06 2016-02-16 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion process
WO2019199571A1 (en) 2018-04-11 2019-10-17 Lummus Technology Llc Structured packing for catalytic distillation
RU2778127C1 (ru) * 2021-11-24 2022-08-15 Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" Способ получения метил(этил)-трет-бутилового эфира

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69123223T2 (de) * 1990-11-07 1997-03-13 Chemical Res & Licensin Prozess zur Herstellung von MTBE
DE10250468A1 (de) * 2002-10-30 2004-05-19 Basf Ag Verfahren zur Herstellung von Oligomeren abgeleitet von Butenen

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US4215011A (en) * 1979-02-21 1980-07-29 Chemical Research And Licensing Company Catalyst system for separating isobutene from C4 streams
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US4302356A (en) * 1978-07-27 1981-11-24 Chemical Research & Licensing Co. Process for separating isobutene from C4 streams
US4242530A (en) * 1978-07-27 1980-12-30 Chemical Research & Licensing Company Process for separating isobutene from C4 streams
US4250052A (en) * 1978-09-08 1981-02-10 Chemical Research & Licensing Company Catalyst structure and a process for its preparation
US4307254A (en) * 1979-02-21 1981-12-22 Chemical Research & Licensing Company Catalytic distillation process
US4232177A (en) * 1979-02-21 1980-11-04 Chemical Research & Licensing Company Catalytic distillation process
US4215011A (en) * 1979-02-21 1980-07-29 Chemical Research And Licensing Company Catalyst system for separating isobutene from C4 streams
US4336407A (en) * 1980-02-25 1982-06-22 Chemical Research & Licensing Company Catalytic distillation process
US4475005A (en) * 1981-04-10 1984-10-02 Snamprogetti S.P.A. Process for preparing tertiary alkyl ethers
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US4439350A (en) * 1982-06-21 1984-03-27 Chemical Research & Licensing Company Contact structure for use in catalytic distillation
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US4847431A (en) * 1988-03-08 1989-07-11 Institut Francais Du Petrole Process for manufacturing a tertiary alkyl ether by reactive distillation
US4847430A (en) * 1988-03-21 1989-07-11 Institut Francais Du Petrole Process for manufacturing a tertiary alkyl ether by reactive distillation

Cited By (34)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5550298A (en) * 1988-09-02 1996-08-27 Sulzer Brothers Limited Device for carrying out catalyzed reactions
US5262576A (en) * 1989-03-23 1993-11-16 Chemical Research & Licensing Company Method for the alkylation of organic aromatic compounds
US5221441A (en) * 1989-03-23 1993-06-22 Chemical Research & Licensing Company Method for operating a catalytic distillation process
US5120403A (en) * 1989-03-23 1992-06-09 Chemical Research & Licensing Company Method for operating a catalytic distillation process
US5447609A (en) * 1990-02-06 1995-09-05 Koch Engineering Company, Inc. Catalytic reaction and mass transfer process
US5914011A (en) * 1990-02-06 1999-06-22 Koch-Glitsch, Inc. Catalytic reaction and mass transfer structure
US5113015A (en) * 1990-11-20 1992-05-12 Amoco Corporation Recovery of acetic acid from methyl acetate
US5149892A (en) * 1991-10-22 1992-09-22 Ppg Industries, Inc. Chlorinated benzenes
EP0556025A1 (de) 1992-02-10 1993-08-18 Chemical Research & Licensing Company Selektiven Hydrierung von C5-Schnitten
US5609654A (en) * 1992-06-02 1997-03-11 Mobil Oil Corporation Process for hydroisomerization and etherification of isoalkenes
US5489719A (en) * 1992-06-02 1996-02-06 Mobil Oil Corporation Process for the production of tertiary alkyl ether rich FCC gasoline
WO1994008681A1 (en) * 1992-10-16 1994-04-28 Koch Engineering Company, Inc. Catalytic reaction and mass transfer structure and process employing same
US5248837A (en) * 1992-10-21 1993-09-28 Chemical Research & Licensing Company Method for controlling catalytic distillation etherifications
US5565068A (en) * 1994-02-28 1996-10-15 Texaco Development Corporation Energy conservation during plural stage distillation
AU679876B2 (en) * 1995-07-26 1997-07-10 Phillips Petroleum Company A method for improving the recovery of ethanol contained in an etherification reaction zone product stream
US5777187A (en) * 1996-02-08 1998-07-07 Huntsman Petrochemical Corporation Two-step process for alkylation of benzene to form linear alkylbenzenes
US6133492A (en) * 1996-02-08 2000-10-17 Huntsman Petrochemical Corporation Alkylation of benzene to form linear alkylbenzenes using fluorine-containing mordenites
US6166281A (en) * 1996-02-08 2000-12-26 Huntsman Petrochemical Corporation Alkylation of benzene to form linear alkylbenzenes using fluorine-containing mordenites
US5770782A (en) * 1996-02-08 1998-06-23 Huntsman Petrochemical Corporation Process and system for alkylation of aromatic compounds
US5628880A (en) * 1996-02-12 1997-05-13 Chemical Research & Licensing Company Etherification--hydrogenation process
US5919989A (en) * 1996-07-16 1999-07-06 Catalytic Distillation Technologies Etherification process
US20060290016A1 (en) * 2002-02-22 2006-12-28 Catalytic Distillation Technologies. Liquid-continuous column distillation
US7287745B2 (en) 2002-02-22 2007-10-30 Catalytic Distillation Technologies Liquid-continuous column distillation
US20060235092A1 (en) * 2002-02-22 2006-10-19 Catalytic Distillation Technologies Liquid-continuous column distillation
US6846959B2 (en) 2002-10-07 2005-01-25 Air Products And Chemicals, Inc. Process for producing alkanolamines
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EP0405781B1 (de) 1994-08-10
JP2807314B2 (ja) 1998-10-08
MX167454B (es) 1993-03-23
JPH0338539A (ja) 1991-02-19
DE69011434T2 (de) 1994-12-08
DE69011434D1 (de) 1994-09-15
ES2057407T3 (es) 1994-10-16
EP0405781A1 (de) 1991-01-02
KR0148013B1 (ko) 1998-08-17
KR910000203A (ko) 1991-01-29

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